Tertiary butyl alcohol-formaldehyde condensation product and method for preparing the same



' Patented as. 9, .1943

UNITED, STATES wrrau'r OFFICE TERTIARY BUTYL ALCOHOL-FORMALDE- HYDE CONDENSATION PBODUUI AND METHOD FOR PREPARING THE SAME Mortimer" T. Harvey, East Orange, N. 1., asstgnor' to Barrel Research 01 New Jersey No Drawing.

patent to Ellis, 2,143,870, the patentee describes the treatment under anhydrous conditions of tertiary butyl alcohol with trioxymethylene in the presence of hydrochloric acid, and claims to have obtained di-tertiary butyl formal.

I have discovered that novel products may be obtained by employing new methods of treating a tertiary alcohol with formaldehyde.- Accord- 'ing to my novel methods, tertiary butyl alcohol may be treated with an aqueous solution of formaldehyde in the presence of a mineral acid. By employing these methods, I have found that one mole of tertiary butyl alcohol will completely react with more than one mole and with as high as about four to seven moles of the formaldehyde in aqueous solution. In the course of my experimentations, I have discovered that when a mixture of tertiary butyl alcohol and aqueous solution of formaldehyde is heated in the presence of a catal'ystsuch as a mineralacid, the

formaldehyde'and the alcohol react to produce I a product which continues to react with the formaldehyde notwithstanding the presence of unreacted alcohol. This reaction continues until more than one mole of the formaldehyde has completely reacted with one mole of tertiary butyl alcohol, where the'mole ratio of formaldehyde to the alcohol is greater than one and even in those cases where equimolecular proportions of the alcohol and formaldehyde are used and also in those cases where the alcohol and femaldehyde in aqueous solution were present in the ratio as low as 'two to one. According to this invention, it has been found preferable to employ one to eight moles of formaldehydein aqueous solution to one mole of tertiary butyl alcohol.

When the eight or more. moles of formaldehyde in aqueous solution was employed with one nfole 'of tertiary butyl alcohol, it was .found that it was in excess of that which would react with the alcohol and therefore a proportion thereof was present at the end of the reaction period.

' line.

rporation, a corporation Original application October 10, 1942, Serial No. 481,597. Divided and this application October 10, 1942, Serlal No. 461,598

6 Claims. (Cl. 260-638) of makin I The methods of the present invention and the products thereof can be-disclosed best by showing how they are produced, for which the following are given as illustrative examples.

Example 1.-One mole of formaldehyde and one mole of tertiary butyl alcohol at atmospheric Pressure.

. Grams 40% water solution HCHO 425 Tertiary butyl alcohol ml. 370 sulphuric acid The formaldehyde, tertiary butyl alcohol, sulphuric acid and water in the above listed amounts were dissolved together and heated to boiling under a reflux condenser for about six hours, after which the reaction mixture was neutralized with forty grams of sodium hydroxide.

tion above C. contained the hydroxyl group and had a pleasant odor. It was soluble in alcohol, benzene and water and insoluble in gaso- A fraction between 230- C. and 250 C. contains the hydroxyl group, has a pleasant odor and an analysis forcarbon, hydrogen. and oxygen gave the following results:

Per cent 0 78.03 H 10.9! 0

By difference.

This analysis closely approximates the empirical formula CoHmO. I,

Example 2.-One mole of formaldehyde and one mole of tertiary butyl alcohol at a pressure'oi about one hundred pounds per square inch.

- a Grams solution ECHO 510 Tertiary butyl alcohol", 444 sulphuric. acid-. 100

The above three materials in the amounts stated were dissolved togethenplaced in an autoclave .and heated at'a pressure of about one hundred 450 pounds for about .three hours, and the. reaction products neutralized with sodium hydroxide, or

neutralized with potassium carbonate, the resulting topoily layer separated from the water solution, and was distilled. A fraction, boiling up to about 120 C. and containing tertiary butyl alcohol, represented about two-thirds of the total theoretical yield, and had a specific'gravity of 0.888. This fraction dissolves ethyl cellulose and cellulose nitrate very readily and can be used as a solvent for these materials. It can also be used in combination with other solvents such as acetone, phthalates and so on-i'or lacquer solvents. Even though this fraction contains tertiary butyl alcohol theabove solubility property shows the solvent power of these alcohol-formaldehyde reaction products. The fraction between '150- 175' C. gives increased solubility over the lower boiling fraction. Even the material which has been-reacted to the stage where it is not soluble in water also shows extreme solvent actiontoward nitrates, cellulose 'ethers and cellulose.ace-

tate. Where the boiling point is extremely high this solubility may be made use of as a plasticizer for the above mentioned materials together with resins, oils, varnishes and the like. The higher boiling fractions have a very pleasant odor and may be used as perfume bases, plasticizers for rubber, leather goods, phenolic resins, etc. The fraction taken between 150 C. and 175' C; on analysis gave the following:

Per cent tains hydroxyl group, and analysis shows the following:

Per cent 0 59.34 10.88 0

' By diiferenee.

T 'lhisanalysiscloselyapproximatestheempiricsl formula CiaHaOe.

Emple 3.--Two moles of formaldehydesnd one mole pressure.

- Grams 40% water solution ECHO 426 Tertiary butyl alcohol 185 sulphuric acid 122 'lhe'above'three materials in the amounts stated of tertiary butyl alcohol at atmosphericwere dissolved together and'refluxed at the boil-v ing 'pointof the mixture-for about six hours,

' neutralixed'andtlm top oily layer separated from the bottom water layer as described in examples above. No formaldehyde was detected after the reaction. Thetoplayer-wasoily in appearance andtothefeel andhad'aspeciiic gravity of 1.02.

trample 4.Two moles of formaldehyde and monemoleoftertiarybutyl-alcoholn a preasure -'l'heabovethreematerlalsintheamountsstated were di-olved togethenplaood'in aniantoclave at-a pressure of about me hundred pmmdspersqTiareinehforaboutthreehouraaud arated fromthe water layer and distilled. Fractions taken between 200 C. and 270 C. had speciflc gravitiesot from 1.03 to 1.06. They were all soluble in alcohol, benzene, and water but were I insoluble in gasoline.

Example 5.Th ree moles of formaldehydeand The above three materials, in the stated amounts.

were dissolved together and heated to boiling under a reflux condenser for about three hours, at

which time all odor of formaldehyde had disappeared. The reaction mixture was neutralized with about eighty grams of sodium hydroxide.-

and the reaction products which rose to the top were separated from the bottom layer of salt solution, dehydrated with sodium carbonate and distilled in vacuum (about 10 mm. of mercury). v

A out which distilled between 215' C.- and 280 C. (atmos. press.) had a specific gravity of 1.09. It

. was soluble in alcohol, benzene and water, but

was insoluble in gasoline. I

Example 6.Three moles of formaldehyde and one mole of tertiary. butyl alcohol at atmospheric pressure.

40% water solution ncno.. 25s Tertiary butyl alcohol 74 Hydrochloric a The above three materials, in the stated amounts,

were heated to boiling under a reflux condenser for .about six hours. Alter neutralising the reaction mixture, an upper oily layer was separated from a bottom water layer, dehydrated and distilled. A cut distilling between 1'15- C. and 260 C, gave on anaLvsis: x

Per cent By dilerenee.

This closely approximates the emplrical formma I CuHasOs.

rmpu 7.Three molu of formaldehyde" and. one mole of tertiary butyl alooholat atmospheric 40% water solution acne--. m Tertiary m1 alcohol v m 50% sulphuric acid 'l heabovethreemateriahintheamoimtsstatod, were heated to boiling imder a reflux condenser for about six hours atwhich time alltraoes of' formaldehyde had disam'eared. After neutrali ingthereaction mixture,-an upper oily layerwas separated from a bottom water layer eontainlng the salts formed by nentralixatiom'dehydrated and distilled. A eut'taken C(Ild 200' C. (atmospheric pressure) gave'the following aim r This camoa,

Grams approximatesi -the. emph'ical m an; of

- oil.

Example 8.Three moles of formaldehyde and one mole of tertiary butyl alcohol at about one hundred pounds pressure per square inch.

Grams 40% water solution HCHO 765 'Tertiary butyl alcohol 222 I 50% sulphuric acid The above three'materials, in the stated amounts,

were heated under a reflux condenser for about three hours, neutralized and the oily top layer separated and dehydrated, similarly to the treatment in the above examples.

Example 9.Nine moles of formaldehyde and one mole of tertiary butyl alcohol at about one hundred pounds pressure per square inch.

40% water solution HCHO' grams 720 Tertiary butyl alcohol do 74 Sulphuric acid (conc.)

cubic centimeter 0.75

The above three materials, in the stated amounts, were heated in an autoclave to one hundred pounds per square inch pressure and held there for one hour. perature. Some odor of formaldehyde still remained. There was no separation of layers. Ac-

cordingly, after neutralization, the mixture was subjected to fractional distillation at atmospheric pressure. The residue above 135 C. was a viscous By removing by distillation from each of the products produced by following Examples 1 to 9. the fraction having a boiling point as high as 135 0., the remaining product in each case is of an oily nature and is soluble in ethyl alcohol and benzene and at least partially soluble in water but substantially insoluble in gasoline. By removing by distillation from each of said remaining products that fraction having a boiling point as high as 250 C., the remaining fraction is also soluble in ethyl alcohol and benzene. While each of these remaining fractions is par- It was then cooled to room ter'n- 4 alcohol in the method of this invention.

The specific gravities oi the products boiling above 135 C. obtained by the method of this invention areall close to, or greater than one, whereas the formals of alcohols having from four to six carbon atoms which have been described in the literature, all havev specific gravities below 0.85. Thus, according to Arnhold in "Annalen' der Chemie vol. 240, P e 203, (1887), the formal of isobutyl alcohol has a density 01' 0.284 and isoamyl. alcohol a density In addition, there is the diflerence in solubility in petroleum hydrocarbons. The products obtained by this invention, boiling above 135 C. are almost totally insolublein gasoline whereas the formals of the lower alcohols are appreciably soluble in gasoline. This was detially soluble in water, it is less soluble than said remaining product from .which it was obtained.

Although most of the examples presented have utilized sulphuric acid as the mineral acid condensing agent, it has been found that hydrochloric acid can be substituted for the sulphuric acid with no change in either the yield or the properties of the products obtained as shown, by a comparison of Examples 6 and 7. There is one exception to this statement. Lighter I coloredjproducts have resulted from the use of sulphuric acid. The quantity of acid used, it will be noted, varies considerably with the pressure under which the reaction is carried out. At pressures greater than atmospheric -pressure much less acid need to be used and lighter colored products are possible.

.The most important factor, as regards percentage yield of higher boiling material, as well as specific gravity, is the ratio of formaldehyde to the tertiary alcohol. When the mole ratio of the formaldehyde to the alcohol is as great as about 3 to l, the yield of the products boiling above 135 C. is greater than 100% of the quantity of .the alcohol originally present.

The higher boiling products obtained by the methods of this invention are new materials and of unknown chemical composition. That they are not merely formals is evidenced from a consideration of the properties of the products obtained and also from the observation that larger amounts of formaldehyde than even equal vinyl alcohol. Although the water solubility of some of the products may bea disadvantage in their use as plasticizers or assolvents for various plastics, in other instances where extreme oil resistance is desired, their use is decidedly beneficial. Furthermore. these materials can be made water insoluble without changing their other solvent characteristics by an acylating reaction such as by reaction with acetic anhydride, butyric anhydride, etc.

All of the organic condensation products and all fractions thereof produced in the manner hereindisolosed are soluble in ethyl alcohol and benzene and are substantially unaffected by hot dilute mineral acids. And, a yield of condensation products as great as and more than about 100% of the quantity of tertiary alcohol originally present is obtained by said methods when the mole ratio of theformaldehyde in aqueous solution to the tertiary alcohol used is as great as about 3 to 1.

I claim: I

1. Themethod for producing an organic condensation product being substantially unaflected by hot dilute mineral acid and soluble in ethyl alcohol, comprising heating together from one to eight moles of formaldehyde in aqueous solution and one mole of tertiary butyl alcohol in the presence of amineral acid until such product is formed.

2. The method for making an organic condensation product soluble in ethyl alcohol and being unafiected byhot dilute mineral acid and whose yield is as great as about of the quantity of tertiary butyl alcohol originally present, comprising heating until said product is obtained at said yield tertiary butyl alcohol andan aqueous solution of formaldehyde in the presence of a mineral. acid, the mole ratio of the I formaldehyde in said solution to said tertiary butyl alcohol being at least as great as about Sta 1. v 3. The method for making an organic condensation product being soluble in ethyl alcohol and being substantially unaffected by dilute molecular proportions are condensed with the mineral acid, which comprises in the presence or a mineral acid completely reacting one mole of tertiary butyl'alcohol with more than one mole ortormaldehyde in aqueous solution.

4. The method of making condensation products, which'comprises heating together from one to eight moles of formaldehyde in water solution and one mole of tertiary butyl alcohol, in

the presence or a mineral acid, and removing I therefrom'the portion of the condensation products boiling below about 135' C.

5. A product having fractions whose boiling 10in the presence of a mineral acid;

"points are above 135' C. and obtainedbyheating together from one toreight moles of formaldehyde in water solution and one mole of tertiary butyl alcohol, in the presence of a mineral acid. a 

